Polymerization catalysts and preparation thereof



Patented May 4. 1948 POLYMERIZATION CATALYSTS AND PREP- ARATION THEREOF Charles A. Kraus, Providence, R. I., and John D. Calfee, Manhasset, N. Y., assignors to Standard Oil Development Company, a corporation of Delaware N Drawing. Application October 4 1944, Serial No. 557,218

4 Claims. 1

This invention relates to catalytic polymerization processes; relates particularly to Friedel- Crafts catalyst complex substances and relates especially to Friedel-Crafts catalyst in the form of composite or complex salts of aluminum chloride with aluminum alkoxides in solution in appropriate solvents, to yield catalyst solutions of relatively high concentration suitable for polymerization and condensation reactions.

In the conducting of polymerization and condensation reactions, 'difficulty has been experienced in the finding of adequate and satisfactory catalysts which will cause the desired reaction to proceed in the desired way and to yield the desired product. It has been found that for many catalytic reactions for the polymerization and condensation of organic substances, aluminum chloride is a potent and powerful catalyst, but the very low solubility of aluminum chloride in organic solvents generally, sharply limitsits useiulness, especially for low temperature reactions toyield solid polymers, since the low solubility of aluminum chloride limits its sphere of activity; and the tendency to form a covering of solid polymer around each grain of solid aluminum chloride, through which the aluminum chloride does not pass, results in many cases in the complete uselessness of the aluminum chloride as a catalyst.

It has been found that aluminum chloride is somewhat soluble in the lower alkyl halides, and very valuable and important reactions have been obtained by the use of such solutions. However, the solubility at saturation in these liquids is so low that for many reactions an insufiicient 5 amount of catalyst can be gotten into the site of the reaction, or the amount of solvent necessary to carry the required weight of catalyst is so great-as to interfere with the progress of the reaction.

According to the present invention, a catalyst of high solubility characteristics is prepared by combining aluminum with an alcohol to yield the metal alkoxide or alcoholate, which in turn is then combined with a substantial portion of aluminum chloride to yield a complex or alkoxy halide. This complex salt is characterized by a relatively very high solubility in a wide range of solvents, both aliphatic and aromatic; especially in the hydrocarbons and in the halo-substituted hydrocarbons.

The process of the invention provides a, new and highly soluble complex or composite Friedel- Crafts type catalyst of high potency and relatively high solubility in a. wide range of solvents. Other objects and details of the invention will be apparent from the following description.

In practicing the invention the composite catalyst is prepared by reacting aluminum with an alcohol, under such conditions as to produce an alkoxide or aryl oxide of the aluminum; and the resulting compound is then combined with a similar metal halide to form a complex Friedel- Crafts active metal alkoxy halide catalyst. The resulting substance may be solid or liquid according to the halide chosen and according to the aryl radical chosen. The compound further shows a relatively high solubility in such substances as the lower liquid hydrocarbons, in the alkyl halides, in benzene and its homologues, in carbon disulfide and its homologues, in the aromatic hydrocarbons in general, whether halogenated or not, and in a wide variety of similar oxygenfree liquid solvents.

Example 1 The first step in the process of the invention is the preparation of aluminum alkoxide, in the present example, aluminum ethoxlde. For this purpose, aluminum metal in the form of fine shavings was washed with dilute hydrochloric acid, then with. dilute sodium hydroxide solution, then thoroughly rinsed with water, then with alcohol, and then with ether; and thereafter dried under vacuum. parts by weight of the clean aluminum (with a minimum of exposure to atmospheric oxygen). was placed in a container along with 650 parts by weight 01. anhydrous xylene and the container-was fitted with dropping vessel and reflux condenser. The xylene was brought to boiling, and to the mixture there was then added 450 parts by weight of absolute alcohol, together with 0.4 part by weight of mercuric chloride. The material'was added slowly, dropwise, and care was taken to avoid an excess of alcohol as indicated by the formation of insoluble alcoholates. Sufficient heat was applied to the container to maintain the contents in vigorous ebullition, the vaporized xylene being condensed and returned to the reactor. The alcohol was added over a period of several hours and the boiling under reflux conditions was continued (preferably in all'glass equipment).

\ ammo until the reaction ceased. The resulting solution was illtered to remove residual particles of ahnnlnum, the alone was boiled oil, and the ethoxide was distilled under reduced pressure The boiling point varied from about 175 C. to 180 C. at 3 millimeters pressure of mercury. The yield was approximately 70% on the aluminum.

The purified aluminum ethoxy compound auoctmn was then pulverized and mixed with powdered aluminum chloride in a molar ratio of one part or the ethoxide to three parts the aluminum chloride. The materials were mixed together in a container vented through a calcium chloride tube and cooled by water applied to the exterior oi. the container to prevent undue heating: and the development of an unduly vigorous,

reactlom. After a relatively short time, about half oi the material was converted to a liquid. The container was then connected to a drying train and heated on an oil bath at 150 0., and the mixture stirredfintil substantially all of the residual solld aluminum chloride had dissolved. Only a brief immersion in the oil bath. was required for this step of the operation. As th'elast.

of the aluminum chloride dissolved, the evolution of small bubbles oi ethylchloride was noted, and

the reaction mixture was cooled promptly to minimize 'the formation of ethyl. chloride. The catalyst material as prepared is a dark red, limpid liquid. stream temperature. which is highly soluble in the halogenated hydrocarbons, CSaand aro-..

matic hydrocarbons. The material appears to be a composite catalyst having the form of Al (OCaI-Is) 3.3A1Cla Example 2 50 parts by volume of liquid-propylene were diluted with 100 parts by volume of methyl chloride and cooled to --78 C., by vigorous stirring in a container surrounded by a cooling jacket consisting of solid carbon dioxide and isopropyl alcohol.

To this cooled mixture there were then added 2 parts .by volume of the liquid composite or complex catalyst prepared in Example 1'. The reace 7 tion mixture stood without perceptible change for approximately minutes, then a rapid P lymerization reaction occurred, the heat of reaction be-- ing suillcient to cause a vigorous boiling of the, reaction mixture. After the reaction had ceased and heat was no longer evolved, the catalyst was destroyed by the addition to the mixture oi a small quantity of propyl alcohol. The reaction mixture was then dissolved in petroleum ether to volatilize out the methyl chloride and residual propylene; and the solution in petroleum. ether was washed with water. The petroleum ether was then evaporated, leaving a clear, highly vis-' 1 cous oil. This oil was a moderately high molecu-.

lar weight P lymer of propylene, of about 10,000

molecular weight (Staudinger). The polymer is useful-as an insulating oil and as a tacki'fierior snythetic rubber.

' Example 3 6 parts by weight of the composite catalyst prepared in Example 1 were mixed with parts by weight of methyl bromide at 23 C, Ethylene and; hydrogen chloride in .cquimolar quantities were then bubbled through the catalyst-methyl bromide mixture. A rapid reaction occurred and introductionoi the gases wa continued as lon as the reaction continued at a good speed. Upon warming the reaction mixture, 55 parts by weight of ethyl chloride were recovered.

Example 4 The catalyst is eillcient and effective for the alkylation oi benzol. l0 parts by weight of the catalyst of Example 1 were dissolved in 50 parts by weight of benzol at room temperature. Ethyl Example 5 v The catalyst is also eilective for the alkylation oi. isobutane, or the combination of ethylene and isobutane. 11 parts by weight of the catalyst of Example 1 were dissolved in 20 parts by weight of methyl bromide and an equal volume of isobutane was added, and the mixture was cooled to -33 C. Ethylene was then bubbled into the solution, maintaining the temperature at 33 C., meanwhile keeping the solution conditions as nearly the same as possible by adding two volumes of isobutane for each volume of ethylene condensed. The solubility of the catalyst gradually decreased and it separated out as a dark red oil during the course of the reaction. As the precipitation of catalyst neared completion, the absorption of ethylene diminished to a negligible amount. The material was separated from the precipitated catalyst, washed and iractionally distilled. Approximately 20% of the material added was obtained as an addition product in the form of 2,3 diethyl butane. The remainder consisted of more highly alkylated compounds and a portion of polymerized ethylene.

Example 6 I A mixture was prepared consisting of appr ximately parts by weight of isobutylene of 8% purity and 20.partsby weight of butadiene of 96% purity. This material was-cooled to a temperature between 100 C. and -103 C. by the additionv of approximately 3 volumes of liquid ethylene per vvolume of mixed olefins. To the mixture therewas then added a catalyst in the form of a solution of the catalyst as prepared in Example 1 in solution in methyl chloride in 0.7% concentration; the catalyst solution being added in the form of a fine spray onto the surface of the ra dly stirred olefinic mixture. The poly- -mer i'zati n proceeded rapidly to yield a solid polymer. The solid polymer was removed from the reaction mixture, brought up to room temperature and washed on the mill to remove as much as possible of the catalyst and the volatile components.

The washed and dried polymer was then compounded acccrding to the following recipe:

' Parts Polymer 100 Zinc oxide- 5 Stearic acid 3 Carbon black 10 I 'Suli'ur' I w 2 TUADS (tctramethyl thiuram disulfide) 1 Samples of the compounded polymer were then cured for 30 minutes and 60 minutes, and tensile strength and elongation at break were determimic}i to yield the following test inspection reco Evaluation of Pure Gum Stocks Cured at 307 C.

' Catalyst Tensile Strength Conv Elongation Run 1..

Run 2-- 0.77 Al(6ClHI)I-3A1Cll in M601.

These results show the potency of the catalyst and its efllcient operation.

The above examples deal only with aluminum ethoxide in combination with aluminum chloride. The reaction is equally applicable for the formation of a. catalyst consisting of aluminum methoxide with aluminum chloride; and the formation of aluminum propoxide and aluminum chloin, and mixability with, a relatively large num- 36 her of solvents and reactive liquid components.

The Friedel-Crafts active metal halides referred to above may be any or those listed in the article by N. O. Galloway entitled The Friedel-Crafts Synthesis" published in "Chemical Reviews, i'or 40 Number the American Chemical Society at Baltimore in 1935, vol. XVII, No. 3, beginning at page 327,'the list being particularly well shown in Table 2, page 375 of the article. The Friedel-Craits metal halides there listed are well known to those skilled in the art, comprising AIC'ls, AlBn, SbCls, SbCl.-,, BFa, FeCla, BnCh, NaCl-AiCla. TiCh, Tick. ZrCli ma znchl While there are above disclosed but a limited number of embodiments of the catalyst and process of the invention, it is possible to produce still other embodiments without departing from the inventive concept herein disclosed and it is therefore desired that only such limitations be imposed on the appended claims as are stated therein or required by the Prior art.

The invention claimed is:

1, A composition of matter consisting essentially of aluminum alcoholate and aluminum chloride in a 1 to 3 molar ratio, said composition being a double salt complex having a low melting point and a high solubility in alkyl halides, carbon disulfide, and hydrocarbons.

2. A catalyst for polymerizing unsaturated hydrocarbons at temperatures below 0 C. consisting essentially of aluminum alcoholate and a Friedel-Crafts active metal halide in 1 to 3 molecular proportions dissolved in an alkyl halide solvent in a concentration of the order of 9.7%.

3. The chemical process which comprises the steps of reacting together aluminum metal and an alcohol to yield an aluminum alcoholate, and adding to 1 molar part of said alcohola'te 3 molar parts of a Friedel-Crafts active metal halide to yield a homogeneous complex characterized by a low melting point and a high solubility in alkyl halide, carbon disulfide, and hydrocarbons.

4. A chemical process as in claim 3 wherein said halide is aluminum chloride. 1

CHARLES A. KRAUS. JOHN D. CALFEE.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENT Name Date 1,459,852 Mugdan et al (June 26, 1923 1,671,517 Edeleann May 29, 1928 1,793,935 Kaufler et al. Feb. 24, 1931 2,144,816 Schaad Jan. 24, 1939 2,276,893 Thomas et a1. Mar. 17, 1942 2,300,069 Skooglund Oct. 27, 1942 2,329,858 Schmering Sept. 21, 1943 

